FR2825702A1 - COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A DIAZOIC DYZOIC SPECIFIC DICATIONIC DYE - Google Patents

Abstract

The invention concerns a dyeing composition for dyeing keratinous fibres, in particular human keratinous fibres and more particularly hair, comprising a dicationic diazo dye of formula W1-N=N-W2-N=N-W3 as well as the dyeing method using same and the novel compounds of formula (I).

Description

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COMPOSITION FOR DYEING KERATINIC FIBERS
INCLUDING A DIAZO COLOR) AS SPECIFIC DICATIONIC
The subject of the invention is a new dye composition for dyeing keratin fibers, in particular human hair, containing a particular dicationic diazo dye, as well as the process for dyeing keratin fibers using such a composition. Another subject of the invention is new diazo dicationic dyes.

 It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, give rise, through an oxidative condensation process, to colored compounds.

 We also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.

 The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.

 This oxidation dyeing process consists in applying to the keratin fibers, oxidation bases or a mixture of oxidation bases and couplers with an oxidizing agent, for example hydrogen peroxide, to leave on, then to rinse the fibers. The resulting colorings are permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing. Generally applied at basic pH, it makes it possible to obtain a dyeing and at the same time a lightening of the fiber which translates in practice by the possibility of obtaining a final coloration lighter than the original color. In addition, the lightening of the fiber has the advantageous effect of generating a solid color in the case of gray hair, and in the case of naturally pigmented hair, of bringing out the color, that is to say making it more visible.

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 It is also known to dye keratin fibers by direct coloring. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for the fibers, to allow to pause, then to rinse the fibers.

 It is known, for example, to use direct dyes belonging to the class of benzene nitrates, anthraquinones, nitropyridines, azo, indoamines, azines or triarylmethanes.

 The resulting colorings are particularly chromatic colors which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing or perspiration. These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair. In addition, their sensitivity to light is dependent on their uniform or aggregate distribution in the keratin fiber.

 It is known to use direct dyes in combination with oxidizing agents. However, direct dyes are generally sensitive to the action of oxidizing agents such as hydrogen peroxide, and reducing agents such as sodium bisulfite, which makes them generally difficult to use in lightening direct dye compositions based on hydrogen peroxide and based on an alkalizing agent or in oxidation dye compositions in combination with precursors of the oxidation base or coupler type.

 For example, it has been proposed in patent applications FR-1,584,965 and JP-062,711,435 to dye the hair with dye compositions based on direct nitro dyes and / or disperse dyes azo and hydrogen peroxide ammonia by applying to the hair a mixture of said dyes and said oxidant, produced just before use. However, the colorings obtained have proved to be insufficiently tenacious and disappear with shampooing, revealing the lightening of the hair fiber. Such coloring becomes unsightly by evolving over time.

There have also been proposed in patent applications JP-53 95693 and
JP-55 022638 to dye hair with compositions based on cationic direct dyes of the oxazine type and ammoniacal hydrogen peroxide, by applying to

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 the hair, in a first step, ammoniacal hydrogen peroxide, then in a second step, a composition based on the direct oxazine dye. This coloration is not satisfactory, due to the fact that it requires a process made too slow by the pause times of the two successive stages. If, on the other hand, an extemporaneous mixture of the direct oxazine dye with ammonia hydrogen peroxide is applied to the hair, it is not colored or at least, a coloring of the hair fiber is obtained which is almost nonexistent.

 More recently, patent application FR 2 741 798 has described dye compositions containing direct dyes comprising at least one quaternized nitrogen atom of the azo or azomethine type, said compositions being to be mixed extemporaneously at basic pH with an oxidizing composition. These compositions make it possible to obtain colorings with homogeneous, tenacious and brilliant reflections. However, they do not make it possible to dye the keratin fibers with as much power as with oxidation coloring compositions.

 There is therefore a real need to look for direct chromatic dyes which make it possible to dye keratin fibers as powerfully as oxidation dyes, which are as stable as they are in light, are also resistant to weathering, washing and perspiration, and moreover, sufficiently stable in the presence of oxidizing and reducing agents to be able to simultaneously obtain a lightening of the fiber either by the use of direct lightening compositions containing them, or by the use of oxidation coloring compositions containing them. There is also a real need to look for direct dyes which make it possible to dye keratin fibers to obtain a very wide range of colors, in particular very chromatic, without forgetting the so-called fundamental shades such as blacks and browns.

Formule (1) These objects are achieved with the present invention which relates to a composition for dyeing keratin fibers, and in particular human keratin fibers such as the hair, comprising at least one diazo dicationic dye of formula (1) below:

Formula 1)

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- W2 représente un groupement aromatique carboné, pyridinique ou pyridazinyle de formule (IV)

formules (II), (III), (IV), dans lesquelles : - Xi représente un atome d'azote ou un radical CR5 - X2 représente un atome d'azote ou un radical CR6 - Z1 représente un atome d'oxygène, de soufre ou un radical NR8, - Z2 représente un atome d'azote ou un radical CRg, - Z3 représente un atome d'azote ou un radical CR12, - Z4 représente un atome d'azote ou un radical CRis, - la liaison a du cycle cationique à 5 chaînons de la formule (II) est reliée au groupement azoïque de la formule (1), - la liaison b du cycle cationique à 6 chaînons de la formule (III) est reliée au groupement azoïque de la formule (1)

- Rs, R4, Re, R6, R7, Rg, Rio, Ru, Riz. Ris. représentent, ensemble ou indépendamment l'un de l'autre, un atome d'hydrogène, une chaîne hydrocarbonée en C1-C16 I linéaire ou ramifiée, pouvant former un ou plusieurs in which - W1 and W3, independently of one another, a heteroaromatic radical represented by the following formulas (II) and (III):

- W2 represents a carbon, pyridine or pyridazinyl aromatic group of formula (IV)

formulas (II), (III), (IV), in which: - Xi represents a nitrogen atom or a radical CR5 - X2 represents a nitrogen atom or a radical CR6 - Z1 represents an oxygen atom, sulfur or an NR8 radical, - Z2 represents a nitrogen atom or a CRg radical, - Z3 represents a nitrogen atom or a CR12 radical, - Z4 represents a nitrogen atom or a CRis radical, - the bond a of 5-membered cationic ring of formula (II) is linked to the azo group of formula (1), - link b of the 6-membered cationic ring of formula (III) is linked to the azo group of formula (1)

- Rs, R4, Re, R6, R7, Rg, Rio, Ru, Rice. Laugh. represent, together or independently of one another, a hydrogen atom, a linear or branched C1-C16 I hydrocarbon chain, which can form one or more

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carbon rings having 3 to 6 members, and which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R3, R4, Rs, R6, R7, Rg, Rio, Ru, R12, R13, containing no peroxide bond, no diazo or nitroso radicals, - R7 with Re, R10 with R11 and R12 with R13 can form an aromatic ring carbonaceous, such as phenyl,
X is an organic or mineral anion.

carbone de la chaîne hydrocarbonée définie pour les radicaux R3, R4, Rs, R6, R7, Rg, Rio. Ru, Ri2, Ris, peuvent être remplacés par un atome d'oxygène, d'azote ou de soufre ou par un groupement S02, et/ou que ces chaînes hydrocarbonées sont insaturées, cela signifie que l'on peut, à titre d'exemple, faire les transformations suivantes :

!-CH-H peut devenu ; 1 2 1 1 1 peut devenir :-0 1 1 I 1 1 - '\ peut devenu'-SO 1 1 S02 1 1 I 0 peut devenir : -O 1 I-CH-CH peut devenir -O-CH 1 2 3 1 3
En particulier, on entend par"chaîne hydrocarbonée ramifiée", une chaîne pouvant former un ou plusieurs cycles carbonés comportant de 3 à 6 chaînons. On entend par chaîne hydrocarbonée insaturée, une chaîne pouvant comporter une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples, cette chaîne hydrocarbonée pouvant conduire à des groupements aromatiques. According to the invention, when it is indicated that one or more of the atoms of

carbon of the hydrocarbon chain defined for the radicals R3, R4, Rs, R6, R7, Rg, Rio. Ru, Ri2, Ris, can be replaced by an oxygen, nitrogen or sulfur atom or by an S02 group, and / or that these hydrocarbon chains are unsaturated, this means that it is possible, as example, do the following transformations:

! -CH-H can become; 1 2 1 1 1 can become: -0 1 1 I 1 1 - '\ can become'-SO 1 1 S02 1 1 I 0 can become: -O 1 I-CH-CH can become -O-CH 1 2 3 1 3
In particular, the term "branched hydrocarbon chain" means a chain which can form one or more carbon rings comprising from 3 to 6 members. The term “unsaturated hydrocarbon chain” is understood to mean a chain which can comprise one or more double bonds and / or one or more triple bonds, this hydrocarbon chain being able to lead to aromatic groups.

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 X is an organic or inorganic anion, for example chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; an alkyl (Ci-Ce) sulphate such as for example a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; a (C1-C6) alkyl sulfonate such as methylsulfonate; an arylsulfonate substituted or unsubstituted by a C1-C4 alkyl radical such as for example a 4-toluylsulfonate.

Plus préférentiellement, R3, R4, R5, R6, Rio, R11, R12, R13 représentent un atome d'hydrogène, un radical alkyle en C1-C4 éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux hydroxy, amino, (di) alkylamino en C1-C2 ; un radical carboxy ; un radical alcoxy en C1-C2 ; un radical amino ; un radical (di) alkylamino en C1-C2 ; un radical (poly)-hydroxyalkylamino en C2-C4
Selon un mode de réalisation particulièrement préféré, R3, R4, R5, Re. Rio, Rn, R12, R13, représentent un atome d'hydrogène, un radical méthyle, phényle, 2hydroxyméthyle, un carboxy, un radical méthoxy, éthoxy, 2-hydroxyéthyloxy, un radical amino, méthylamino, diméthylamino, 2-hydroxyéthylamino. R3, R4, R5, Re. Rio, R11, R12, R13, preferably represent, independently of one another, a hydrogen atom; a linear or branched C1-C4 alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy-C2-C4, amino, (di) C1-C2 alkylamino radicals , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy-C2-C4, amino, (di) C1-C2 alkylamino, carboxy, sulfonic or an atom halogen such as chlorine, fluorine or bromine; a carboxy radical; a sulfonylamino radical; a sulfonic radical; a C1-C2 alkoxy radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a C1-C2 (di) alkylamino radical; a C2-C4 (poly) -hydroxyalkylamino radical

More preferably, R3, R4, R5, R6, Rio, R11, R12, R13 represent a hydrogen atom, a C1-C4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino, (di) radicals C1-C2 alkylamino; a carboxy radical; a C1-C2 alkoxy radical; an amino radical; a C1-C2 (di) alkylamino radical; a C2-C4 (poly) -hydroxyalkylamino radical
According to a particularly preferred embodiment, R3, R4, R5, Re. Rio, Rn, R12, R13, represent a hydrogen atom, a methyl, phenyl, 2hydroxymethyl radical, a carboxy, a methoxy, ethoxy, 2- hydroxyethyloxy, an amino, methylamino, dimethylamino, 2-hydroxyethylamino radical.

 R7 and Rg represent, independently of one another, a hydrogen atom; a linear or branched C1-C4 alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy-C2-C4, amino, (di) C1-C2 alkylamino radicals , carboxy or sulfonic; an optionally substituted phenyl radical; a carboxy radical; a sulfonylamino radical.

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 Among these substituents, Ry and Re preferably represent a hydrogen atom, a phenyl radical, a C1-C4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino, (di) alkylamino C1-C2 radicals, carboxy.

 According to a particularly preferred embodiment,? 7 and Ra preferably represent a hydrogen atom, a methyl, phenyl, 2hydroxymethyl radical, a carboxy.

hydroxy, alcoxy en C1-C2, (poly) -hydroxyalcoxy en C2-C4, amino, (di) alkylamino en d- C2, carboxy ou sulfonique ; un radical phényle éventuellement substitué. R1, R2 and Ra represent a linear or branched C1-C6 alkyl radical, optionally substituted by one or more radicals chosen from the radicals

hydroxy, C1-C2 alkoxy, (poly) -hydroxy C2-C4alkoxy, amino, (di) d-C2 alkylamino, carboxy or sulfonic; an optionally substituted phenyl radical.

 Among these substituents, Ri, R2 and Rg preferably represents a C1-C4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, amino, (di) C1-C2 alkylamino, carboxy, sulfonic acid.

carboxyméthyle, 2- carboxyéthyle, 2-sulfonyléthyle. According to a particularly preferred embodiment Ri, R2 and Re preferably represents a methyl, ethyl, 2-hydroxyethyl, 1-

carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl.

 W1 and W3 preferably represent, independently of one another, a cationic group imidazolinium, triazolinium, thiazolinium, pyridinium substituted by the preferred radicals Ri, Ry Rlo, Rn, R12, R13.

 W2 preferably represents a phenyl or pyridyl group substituted by the preferred radicals R3, R4 Rs, R6.

 The concentration of diazo dicationic dye of formula (1) can vary between 0.001 and 5% by weight approximately relative to the total weight of the dye composition, and preferably between approximately 0.05 and 2%.

 The dye composition in accordance with the invention may also contain direct dyes different from those of formula (1), these dyes being able in particular to be chosen from neutral benzene, neutral, acid or cationic direct dyes, neutral azo acid or cationic direct dyes , quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes,

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les colorants directs aziniques, les colorants directs méthiniques, les colorants directs triarylméthaniques, les colorants directs indoaminiques et les colorants directs naturels.

azine direct dyes, methine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the benzene direct dyes which can be used according to the invention, mention may be made in particular of the following compounds: - 1,4-diamino-2-nitrobenzene - 1-amino-2 nitro-4-p-hydroxyethylaminobenzene - 1-amino-2 nitro- 4-bis (p-hydroxyethyl!) - aminobenzene - 1, 4-Bis (ss-hydroxyethylamino) -2-nitrobenzene -1-p-hydroxyethylamino-2-nitro-4-bis- (P-hydroxyethylamino) -benzene - 1 -P-hydroxyethylamino-2-nitro-4-aminobenzene -1-p-hydroxyethylamino-2-nitro-4- (ethyl) (P-hydroxyethyl) -aminobenzene -1-amino-3-methyl-4-p-hydroxyethylamino- 6-nitrobenzene - 1-amino-2-nitro-4-p-hydroxyethylamino-5-chlorobenzene - 1, 2-Diamino-4-nitrobenzene - 1-amino-2-ss-hydroxyethylamino-5-nitrobenzene -1, 2- Bis- (P-hydroxyethylamino) -4-nitrobenzene -1-amino-2-tris- (hydroxymethyl) -methylamino-5-nitrobenzene - 1-Hydroxy-2-amino-5-nitrobenzene - 1-Hydroxy-2-amino- 4-nitrobenzene - 1-Hydroxy-3-nitro-4-aminobenzene - 1-Hydroxy-2-amino-4, 6-dinitrobenzene - 1-ss-hydroxyethyloxy-2-ss-hydrox yethylamino-5-nitrobenzene - 1-Methoxy-2-ss-hydroxyethylamino-5-nitrobenzene - 1-ss-hydroxyethyloxy-3-methylamino-4-nitrobenzene -1-p, y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene - 1-p-hydroxyethylamino-4-p, y-dihydroxypropyloxy-2-nitrobenzene - 1-P, y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene - 1-ss-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene - 1- P-hydroxyethylamino-3-methyl-2-nitrobenzene - 1-p-aminoethylamino-5-methoxy-2-nitrobenzene -1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene - 1-Hydroxy-2-chloro- 6-amino-4-nitrobenzene

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-1-Hydroxy-6-bis- (f-hydroxyéthyl)-amino-3-nitrobenzène - 1-ss-hydroxyéthylam ino-2-nitrobenzène - 1-Hydroxy-4-ss-hydroxyéthylamino-3-nitrobenzène.

-1-Hydroxy-6-bis- (f-hydroxyethyl) -amino-3-nitrobenzene - 1-ss-hydroxyethylam ino-2-nitrobenzene - 1-Hydroxy-4-ss-hydroxyethylamino-3-nitrobenzene.

Among the azo direct dyes which can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.

Among these compounds, the following dyes may very particularly be mentioned: -3.3-dimethyl-2 chloride - [[4- (dimethylamino) phenyl] azo] -1H-lmidazolium, -1, 3-dimethyl-2- chloride [(4-aminophenyl) azo] -1 H-Imidazolium, - 1-methyl-4-methylsulfate - [(methylphenylhydrazono) methyl] -pyridinium.

One can also cite among the azo direct dyes the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition: - Disperse Red 17 -Acid Yellow 9 -Acid Black 1 - Basic Red 22 - Basic Red 76 -Basic Yellow 57 - Basic Brown 16 -Acid Yellow 36 - Acid Orange 7 - Acid Red 33 - Acid Red 35 -Basic Brown 17 -Acid Yellow 23 - Acid Orange 24 - Disperse Black 9.

Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis- (ss-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid.

Among the quinone direct dyes, the following dyes may be mentioned:

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- 1-Aminopropylaminoanthraquinone - 5-ss-hydroxyéthyl-1, 4-diaminoanthraquinone -2-Aminoéthylaminoanthraquinone -1,4-Bis-(ss,&gamma;-dihydroxypropylamino)-anthraquinone. - Disperse Red 15 -Solvent Violet 13 -Acid Violet 43 - Disperse Violet 1 -Disperse Violet 4 - Disperse Blue 1 -Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Acid Blue 62 - Disperse Blue 7 -Basic Blue 22 -Disperse Violet 15 - Basic Blue 99 as well as the following compounds: -1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone -1-Aminopropylamino-4-methylaminoanthraquinone

- 1-Aminopropylaminoanthraquinone - 5-ss-hydroxyethyl-1, 4-diaminoanthraquinone -2-Aminoethylaminoanthraquinone -1,4-Bis- (ss, &gamma; -dihydroxypropylamino) -anthraquinone.

Among the azine dyes, the following compounds may be mentioned: - Basic Blue 17 - Basic Red 2.

Among the triarylmethane dyes which can be used according to the invention, mention may be made of the following compounds: - Basic Green 1 - Acid blue 9 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Acid Violet 49

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- 2-p-hydroxyéthtyamino-5- [bis- (p-4'-hydroxyéthyt) amino] anitino-1, 4-benzoquinone -2-p-hydroxyéthylamino-5- (2'-méthoxy-4'-amino) anilino-1, 4-benzoquinone -3-N (2'-Chloro-4'-hydroxy) phényl-acétylamino-6-méthoxy-1, 4-benzoquinone imine - 3-N (3'-Chloro-4'-méthylamino) phényl-uréido-6-méthyl-1, 4-benzoquinone imine - 3- [4'-N- (Ethyt, carbamytméthy))-amino]-phényt-uréido-6-méthyt-1, 4-benzoquinone imine. -Basic Blue 26 - Acid Blue 7 Among the indoamine dyes which can be used according to the invention, the following compounds may be mentioned:

- 2-p-hydroxyethtyamino-5- [bis- (p-4'-hydroxyethyt) amino] anitino-1, 4-benzoquinone -2-p-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino -1, 4-benzoquinone -3-N (2'-Chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1, 4-benzoquinone imine - 3-N (3'-Chloro-4'-methylamino) phenyl-ureido-6-methyl-1, 4-benzoquinone imine - 3- [4'-N- (Ethyt, carbamytméthy)) - amino] -phenyt-ureido-6-methyt-1, 4-benzoquinone imine.

Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

The additional direct dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the composition and even more preferably from 0.00! : 10% by weight approximately.

 The composition of the invention may also comprise an oxidizing agent.

This oxidizing agent can be any oxidizing agent conventionally used for bleaching keratin fibers. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and enzymes among which may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases.

The use of hydrogen peroxide is particularly preferred.

 The composition according to the invention can also comprise an oxidation base. This oxidation base can be chosen from the oxidation bases

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classiquement utilisées en teinture d'oxydation, par exemple les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et les bases hétérocycliques.

conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

la N-phényl paraphénylènediamine, la 2-ss-hydroxyéthyloxy paraphénylènediamine, la 2-ss-acétylaminoéthyloxy paraphénylènediamine, la N- (ss-méthoxyéthyl) paraphénylènediamine, la 4-aminophenyl pyrrolidine, le 2-thienyl paraphénylène diamine, le 2-ss hydroxyéthylamino 5-amino toluène et leurs sels d'addition avec un acide. Among the paraphenylenediamines, mention may more particularly be made, for example, of paraPhenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2, 3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2, 6-diethyline paraphenyl , 2, 5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (ss-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (sshydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (ss-hydroxyethyl) amino 2-chloro aniline, 2-ss-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (ss-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine - (4'-aminophenyl) paraphenylenediamine, di hydroxypropyl) paraphenylenediamine, N- (ethyl, ss-hydroxyethyl) paraphenylenediamine, N- (ss, &gamma; -

N-phenyl paraphenylenediamine, 2-ss-hydroxyethyloxy paraphenylenediamine, 2-ss-acetylaminoethyloxy paraphenylenediamine, N- (ss-methoxyethyl) paraphenylenediamine, 4-aminophenyl pyrrolidine, 2-thienyl paraphenylenediamine paraphenyl 5-amino toluene and their addition salts with an acid.

paraphénylènediamine, la paratoluylènediamine, la 2-isopropyl paraphénylènediamine, la 2-ss-hydroxyéthyl paraphénylènediamine, la 2-ss-hydroxyéthyloxy paraphénylènediamine, la 2, 6-diméthyl paraphénylènediamine, la 2, 6-diéthyl paraphénylènediamine, la 2, 3-diméthyl paraphénylènediamine, la N, N-bis- (sshydroxyéthyl) paraphénylènediamine, la 2-chloro paraphénylènediamine, la 2-ss-acétylaminoéthyloxy paraphénylènediamine, et leurs sels d'addition avec un acide sont particulièrement préférées. Among the paraphenylenediamines cited above, the

paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-ss-hydroxyethyl paraphenylenediamine, 2-ss-hydroxyethyloxy paraphenylenediamine, 2, 6-dimethyl paraphenylenediamine, 2, 6-diethylenedaphenylenediamenine 3 , N, N-bis- (sshydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-ss-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid are particularly preferred.

 Among the bis-bhenylalkylenediamines, there may be mentioned by way of example, N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N , N'-bis- (ss-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-

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aminophény !) tétraméthytènediamine, ! a N. N'-bis- (p-hydroxyéthyt) N, N'-bis- (4- aminophényl) tétraméthylènediamine, la N, N'-bis- (4-méthyl-aminophényl) tétraméthylènediamine, la N, N'-bis- (éthyl) N, N'-bis- (4'-amino, 3'-méthylphényl) éthylènediamine, le 1, 8-bis- (2, 5-diamino phénoxy)-3, 6-dioxaoctane, et leurs sels d'addition avec un acide.

aminopheny!) tetramethytenediamine,! a N. N'-bis- (p-hydroxyethyt) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'- bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1, 8-bis- (2, 5-diamino phenoxy) -3, 6-dioxaoctane, and their salts addition with an acid.

 Among the para-aminophenols, there may be mentioned by way of example, paraaminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4amino 2- (ss-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluorophenol, and their addition salts with an acid.

 Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.

 Among the heterocyclic bases that may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

 Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- (ss-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

diamine ; la 2, 7-diméthyl pyrazolo- [1, 5-a]-pyrimidine-3, 5-diamine ; le 3-amino pyrazol- [1, 5-a]-pyrimidin-7-ol ; le 3-amino pyrazolo-[1, 5-a]-pyrimidin-5-ol ; le 2- (3-amino pyrazolo-[1, 5-a]-pyrimidin-7-ylamino) -éthanol, le 2- (7-amino pyrazolo-[1, 5-a]-pyrimidin- 3-ylamino)-éthanol, le 2- [ (3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl)- (2-hydroxy-éthyl)amino]-éthanol, le 2- [ (7-amino-pyrazolo [1, 5-a] pyrimidin-3-yl)- (2-hydroxy-éthyl)-amino]- Among the pyrimidine derivatives, mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770
375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine,
2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2,750
048 and among which mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5

diamine; 2,7-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-amino pyrazol- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) - ethanol, 2- [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) amino] -ethanol, 2- [(7-amino-pyrazolo [1 , 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -

<Desc / Clms Page number 14>

 ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] - pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1,5-a ] pyrimidine and their acid addition salts and their tautomeric forms, when there is a tautomeric equilibrium.

 Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- (p-hydroxyethyt) pyrazote, te 3,4-diamino pyrazole, 4,5diamino 1- (4'-chlorobenzyl) pyrazole, 4 , 5-diamino 1, 3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1, 3-dimethyl 5- hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1- (ss-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3methyl pyrazole, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4 , 5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3 -methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4- (ss-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.

aminophénols, les métadiphénols, les coupleurs naphtaléniques et les coupleurs hétérocycliques. The composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibers. Among these couplers, mention may in particular be made of metaphenytenediamines, your meta-

aminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers.

sésamol, le 1-ss-hydroxyéthylamino-3, 4-méthylènedioxybenzène, I'a-naphtol, le 2 By way of example, mention may be made of 2-methyl 5-aminophenol, 5-N- (ss-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3dihydroxy benzene, 2,4-diamino l- (f-hydroxyethytoxy) benzene, 2-amino 4 - (ss- hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1, 3-bis- (2, 4diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene,

sesamol, 1-ss-hydroxyethylamino-3, 4-methylenedioxybenzene, a-naphthol, 2

<Desc / Clms Page number 15>

 methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2 , 6-dimethoxypyridine, 1-N- (ss-hydroxyethyl) amino-3, 4-methylene dioxybenzene, 2, 6-bis- (ss-hydroxyethylamino) toluene and their addition salts with an acid.

 In the composition of the present invention, the coupler (s) are generally present in an amount between 0.001 and 10% by weight approximately of the total weight of the dye composition and more preferably from 0.005 to 6%. The oxidation base (s) are present in an amount preferably between 0.001 to 10% by weight approximately of the total weight of the dye composition, and more preferably from 0.005 to 6%.

 In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

comme le 2-butoxyéthanol, le propylèneglycol, le monométhyléther de propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, et leurs mélanges. The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers

such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

 The organic solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

 The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers,

<Desc / Clms Page number 16>

 cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular anionic, cationic, nonionic and amphoteric associative polymers, antioxidant agents, penetration agents, sequestering agents, perfumes , buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

 The adjuvants mentioned above are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.

 Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, affected by the or the additions envisaged.

 The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.

 Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Ci-C4 ; Re, Ry, Rg et Rg, identiques ou Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:

in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Re, Ry, Rg and Rg, identical or

<Desc / Clms Page number 17>

 different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

 The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

 The invention also relates to a direct dyeing process which comprises the application of a dye composition containing a dye of formula (1) as defined above on keratin fibers. After a pause, the keratin fibers are rinsed leaving colored fibers to appear.

 The application to the fibers of the dye composition containing the azo cationic dye of formula (1) can be used in the presence of an oxidizing agent which causes discoloration of the fiber (direct lightening dye). This oxidizing agent can be added to the composition containing the cationic azo dye at the time of use or directly on the keratin fiber.

 The invention also relates to an oxidation dyeing process which comprises applying to the fibers a dye composition which comprises a dye of formula (1), at least one oxidation base and optionally at least one coupler , in the presence of an oxidizing agent.

 The oxidation base, the coupler and the oxidizing agent are as defined above.

 The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied to the fibers simultaneously or sequentially to the dye composition.

 In the case of oxidation dyeing or lightening direct dyeing, the dye composition is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers. After a pause time of approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.

<Desc / Clms Page number 18>

 The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

 The pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.

 The composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.

 Another object of the invention is a device with several compartments or "kit" for dyeing in which a first compartment contains the dye composition of the invention and a second compartment contains the oxidizing composition. This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

 Finally, the subject of the invention is also the dicationic diazo dyes of formula (1) as defined above.

Claims (28)

1. Composition for dyeing keratin fibers and in particular human keratin fibers such as the hair, comprising at least one dicationic diazo dye of formula (1) below:

 in which - W1 and W3, independently of one another, a heteroaromatic radical represented by the following formulas (II) and (III):

 - Wz represents a carbon, pyridine or pyridazinyl aromatic group of formula (IV)

 formulas (II), (III), (IV), in which: - X1 represents a nitrogen atom or a CRs radical - X2 represents a nitrogen atom or a CRe radical - Z1 represents an oxygen atom, sulfur or a rad! ca) NRs, - Z2 represents a nitrogen atom or a CRg radical, - Z3 represents a nitrogen atom or a CR12 radical, - Z4 represents a nitrogen atom or a CR13 radical, <Desc / Clms Page number 20> X is an organic or mineral anion.  halogens; R3, R4, Rs, Re, R7, Rg, Rio, R11, R12, R13, comprising no peroxide bond, no diazo or nitroso radicals, - R7 with Rg, Rio with R11 and R12 with R13 form a carbon aromatic ring ,

 - the bond a of the 5-membered cationic ring of formula (II) is linked to the azo group of formula (1), - the binder of the 6-membered cationic ring of formula (III) is linked to the azo group of the formula (1) - R3, R4 R5, R6, R7, R9, R10, R11, R12, R13, represent, together or independently of one another, a hydrogen atom, a hydrocarbon chain Ci- Tinear or branched company, which can form one or more carbon rings comprising from 3 to 6 links, and which can be saturated or unsaturated, in which one or more carbon atoms of the carbon chain can be replaced by an oxygen or nitrogen atom or of sulfur or by an SO 2 group, and the carbon atoms of which may be, independently of one another, substituted by one or more atoms  2. Composition according to claim 1 wherein R3, R4, R5, Re. Rio, R11, R12, R13, represent, independently of one another, a hydrogen atom; a linear or branched C1-C4 alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy-C2-C4, amino, (di) C1-C2 alkylamino radicals , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy-C2-C4, amino, (di) C1-C2 alkylamino, carboxy, sulphonic or a d atom 'halogen; a carboxy radical; a sulfonylamino radical; a sulfonic radical; a C1-C2 alkoxy radical; a C2-C4 (poly) hydroxyalkoxy radical; an amino radical; a C1-C2 (di) alkylamino radical; a C2-C4 (poly) -hydroxyalkylamino radical 3. Composition according to claim 2, in which R3, R4, Rg, Rg. Rio, Ru, Ri2, Ris represent a hydrogen atom, a C1-C4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino, (di) alkylamino C1-C2 radicals; a carboxy radical; a C1C2 alkoxy radical; an amino radical; a C1-C2 (di) alkylamino radical; a (poly) - hydroxyalkylamino radical in Cz-C4 <Desc / Clms Page number 21> 4. Composition according to claim 3 in watercolor R3, R4, R5, R6, R10, R11, R12, R13, represent a hydrogen atom, a methyl, phenyl, 2hydroxymethyl radical, a carboxy, a methoxy, ethoxy, 2 -hydroxyethyloxy, an amino, methylamino, dimethylamino, 2-hydroxyethylamino radical.  5. Composition according to any one of claims 1 to 4 wherein R7 and Rg represent, independently of one another, a hydrogen atom; a linear or branched C1-C4 alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy-C2-C4, amino, (di) C1-C2 alkylamino radicals , carboxy or sulfonic; an optionally substituted phenyl radical; a carboxy radical; a sulfonylamino radical.  6. Composition according to claim 5 in which R7 and Rg represent a hydrogen atom, a phenyl radical, a C1-C4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino and (di) alkylamino radicals. Ci-C2, carboxy.  7. Composition according to claim 6 wherein R7 and Rg represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl radical, a carboxy.  8. Composition according to any one of claims 1 to 7 in! aquei) e Ri, Rz and R8 represent a linear or branched C1-C8 alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, (poly) -hydroxy C2-C4alkoxy, amino , (di) C1-C2 alkylamino, carboxy or sulfonic; an optionally substituted phenyl radical.  9. Composition according to any one of claims 1 to 8 in which Ri, R2 and R8 represent a C1-C4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkoxy, amino, ( di) C1-C2 alkylamino, carboxy, sulfonic.  10. Composition according to claim 9, in which R1, R2 and R8

 represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2carboxyethyl, 2-sulfonylethyl radical. 11. Composition according to any one of claims 1 to 10 in which W1 and W3 represent, independently of one another, a cationic group imidazolinium, triazolinium, thiazolinium, pyridinium substituted by the radicals Ri, R7 Rio. R11, Ri2, Ris. <Desc / Clms Page number 22>  12. Composition according to any one of claims 1 to 11 in which W2 represents a phenyl or pyridyl group substituted by the preferred radicals R3, R4 R5, Re- 13. Composition according to any one of claims 1 to 12 further comprising an oxidation base.  14. Composition according to Claim 13, in which the oxidation base is chosen from paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.  15. Composition according to any one of claims 13 or 14 in which the oxidation base or bases are present in an amount between 0.001 and 10%, preferably between 0.005 and 6%.  16. Composition according to any one of claims 1 to 15 comprising at least one coupler.  17. Composition according to claim 16 in which the coupler is chosen

 among metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers and their addition salt with an acid.  18. Composition according to any one of claims 1 to 17 further comprising at least one direct dye different from those of formula (1), chosen from neutral nitrous direct dyes, acidic or cationic, neutral azo direct dyes or cationic, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine direct dyes, methine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.  19. Composition according to any one of claims 1 to 18 further comprising an oxidizing agent, preferably hydrogen peroxide.  20. Process for dyeing keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 to 12 is applied to the fibers.  21. The method of claim 20 wherein the dye composition contains an oxidizing agent. <Desc / Clms Page number 23>  22. The method of claim 21 wherein the oxidizing agent is mixed at the time of use with the dye composition.  23. Method according to any one of claims 21 or 22 in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.  24. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined according to any one of claims 1 is applied to the fibers. 12, further comprising at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.  25. The method of claim 24 wherein the oxidizing agent is mixed at the time of use with the dye composition.  26. The method of claim 24 wherein the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.  27. Multi-compartment device or multi-compartment dyeing "kit", in which a first compartment contains a composition as defined in any one of claims 1 to 18 and a second compartment contains an oxidizing composition.  28. Dicationic diazo compounds of formula (1) as defined according to any one of claims 1 to 12.